Dehydrogenating saturated nitriles to unsaturated nitriles



rsur OFFICE DEHYDROGENATING SATURATED NITRILES TO UNSATURATED NITRILES John W. Tetcr, Chicago, Ill., assignor to Sinclair Refining Company, New York, N. Y., a corporation of Maine No Drawing. Application June 23, 1943, Serial No. 491,937

1 Claim. ((1260-4659) 1 2 This invention relates to the production of tion of nitriles to unsaturated nitriles with a miniunsaturated organic compounds containing nitromum amount of cracking. Molybdenum sulfide. gen and, more particularly, to the dehydrogenain the form of either the disulfide or the trition of nitriles for production of unsaturated sulfide or both, tungsten sulfide, in the form of nitriles. either the disulfide or the trisulfide or both, and Unsaturated nitriles are required for the manunickel sulfide are illustrative of metal sulfides facture of numerous important synthetic prod which may be used in accordance with the invenucts. For example, acrylonitrile is used in proticn. Mixtures of metal sulfides may also be used ducing synthetic rubber. Unsaturated acids and with pa t ul d a esters, produced directly by hydrolysis or alco- The following table illustrates the use of two holysis of unsaturated nitriles, are raw materials spec Catalysts u d n o da ce with the i for numerous synthetic resins. Products readily vention. The specific reaction conditions set obtained from these unsaturated nitriles are vaiuforth therein illustrate reaction conditions Which able for synthesis in the production of pharmamay be used advantageously in accordance with ceuticals, surface coatings, dyes, rubber chemlthe invention, although it must be understood cals, explosives, and the like. that use of the metal sulfide catalysts is by no It is known that nitriles may be dehydrogenmeans limited to these specific conditions. The ated with the production of unsaturated nitriles runs using these t ly s r C pa d in the by contact with suitable catalysts at elevated tem t e h Operations using a non-reducible metal peratures. In general, however, dehydrogenation Oxide ste no -reduc ble metal oxide with catalysts used heretofore has been accom- C a yst emplo in u 1 a d 2 (identified panied by cracking to such an extent as somes e y c mprised 11.90% Cr20s, 85-85% times to completely dominate the dehydrogena- 2 3, gO nd .2 H2O. The sulfide tion. Cracking during dehydrogenation results Catalyst s in run O- 3 a d identified as in production of carbon, volatile hydrocarbons, Catalyst compl'isingamixture of molybdenumhydrogen cyanide and small amounts of ams fi es Co a ng M082 and 32.1% M0 monia, and represents a permanent loss of nitrile Whereas t e s lfid cata yst used in run 4 to the extent that the nitrile is thus consumed. was a mixt re f a j r pr p i n of n sten Dehydrogenation with catalysts such as non-reul and a minor proportion of n ckel sulfide ducible metal oxides may be carried out in a com- Comprising 82, 5.3% WS; and 11.3% NiS. mercially effective manner if cracking is con- In each instance a liquid pr p Product trolled by careful attention to maintenance of omp ising a ut pr pi nitri e, obtained y rather specific reaction conditions of temperature, Chilling Crude propionitrile o about 65 F. and

pressure and space velocity. discarding the lower layer formed during chilling, I have now discovered that a certain type of s passed through a bed of the catalyst at the catalyst may be used for promoting the dehydrotemperature and pressure indicated, the space genation reaction with such a negligible amount V c y e ng e pressed in terms of iqu d olume of cracking that in many instances no traces of of the nitrile charged per hour p r vol me f carbon or of hydrogen cyanide are detectable. catalyst. The volume of the liquid pr duct. 001- The improvement of my present invention in lected at 0 0., was measured and compared with the catalytic dehyrogenation of nitriles for prothe volume of the pro i l f e erminaduction of unsaturated nitriles comprises the tion of the amount of acrylonitrile in the liquid carrying out of the dehydrogenation in the presproduct Was-Ca ri d out y d t g a sample of ence of a catalyst comprising a metal sulfide. the liquid product with water, by adding the The catalyst is advantageously used in pelleted diluted sample toapotassium perm a S form, although the metal sulfides may be used tion and heating the solution, then cooling the eilectively in other physical forms of varying solution and subsequently adding sulfuric acid degrees of subdivision. and potassium iodide, and by titratlng the result- As stated hereinbefore, I have found that metal ing liberated iodide with thiosulfate. The titrasuifides are capable of promoting dehydrogenation was standardized by comparison with synthetic samples containing known quantities of acrylonitrile and propionitrile in various proportions. Determinations of acrylonitrile by this procedure checked closely with determination of acrylonitrile by careful fractional distillation.

Run No 1 2 3 4 italyst A A B C l, 210 l, 220 1. 220 l, 210 1. .13 1.0 1.0 1.0 1.2 1.2 1.2 Vol. percent our-Hg. 86.0 99.0 92.4 97.5 .lcuvloniirile:

Vol. percent in product 21. 5 11.0 18.0 15.0 Moi percent of charge 1 18. 5 ll. 0 16. 0 14. 6 HUN, moi percent oi chg 16. 8 4.6 Hydrogen, ninl port-out of ch 31. 5 11.9 15.0 13. 6 llCN:aL-rylonitrlle. 0.01 0.42

Run No. 1, carried out with a non-reducible metal oxide catalyst at atmospheric pressure, produced acrylonitrile as well as a' substantial amount of HCN, the latter indicating cracking taking place to appreciable extent. Run No. 2, carried out with the same catalyst at a subatmospheric pressure of 100 mm. of mercury so as to reduce the amount of cracking in accordance with my copending application Serial No. 491,936, filed concurrently herewith, now abandoned, gave a much lower ratio of cracking to dehydrogenation. On the other hand, runs Nos. 3 and 4, both carried out with metal sulfide catalysts at substantially the same temperature and pressure, produced somewhat less acrylonitrile than in run No. 1 and more than in run No. 2, but cracking was reduced to such an extent that hydrogen cyanide was not detectable in the reaction product and no observable amount of carbon was formed during the period of operation (1% hours for run No. 3 and 2 hours for run No. 4)

The catalysts of my invention are effective in the catalytic dehydrogenation of other nitriles and produce under a broad range of operating conditions effective yields of unsaturated nitriles with a minimum consumption of the nitriles due to cracking. The catalysts are adapted to dehydrogenate products containing a wide range of amounts of saturated nitriles and thus are efiective in further dehydrogenating the product or a previous run through the catalyst. Continuous operation with recycle of unconverted saturated nitriles may be carried out with advantage with the metal sulfide catalysts.

The catalysts tend to lose their dehydrogenation activity after extensive use, due largely to accumulation of carbon on the catalyst as result of some cracking of the nitriles. The catalysts may be regenerated to their former activity by burning off the carbon in the presence of air, this operation converting the sulfides into their corresponding oxides. The oxides may in turn be converted back to the sulfides by bringing the oxides into contact with hydrogen sulfide, mercaptans, etc., at elevated temperatures of the order of about 1200" F.

I claim:

In the catalytic dehydrogenation of nitriles for the production of unsaturated nitriles, the immovement which comprises carrying out the dehydrogenation in the presence of a catalyst comprising a mixture of a major proportion of tunesten sulfide and a minor proportion of nickel sulfide.

JOHN W. TE'IER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,110,833 Mark et a1. Mar. 8, 1938 2,184,235 Groll et al Dec. 19, 1939 FOREIGN PATENTS Number Country Date 790,262 France Nov. 16, 1935 

